Reduction of carbon formation in hydrocarbon synthesis



- c. H. -HQLDER REDUCTION op CARBON `FoRlvmTIoN 1N HYDRocARBN SYNTHESIS Filed sept. 30, 1948 Feb. 17, 195;?v

Clnica H. Holder' Srivanbor .ESHM Clbborne Patented Feb. 17, 1953 REDUCTION OF CARBON FORMATION IN HYDROCARBON SYNTHESIS Clinton H. Holder, Cranford, N. J.,'assgnor to Standard Oil Development Company, a

ration of Delaware Application September 30, 1948, Serial No. '51,984

The present invention relates to the synthesis of hydrocarbons from carbon oxides and hydrogen in the presence of suitable catalysts. The invention relates more particularly to a process for obtaining high yields of normally liquid hydrocarbons boiling within the gasoline and diesel oil range and concomitantly retarding excessive catalyst fouling and disintegration.

The synthesis of hydrocarbons and other valu able products from gas mixtures containing varparticularly carbon monoxide, both in xed bed as Well as in dense phase iiuid catalyst operation is well known in the art. The character and quality of the'synthesis product depends largely on the temperatures, pressures, H2:CO ratios of the feed gas and the nature of the catalyst used, the latter being usually an iron groupl metal catalyst promoted with such prometers as various alkali metal compounds, rare earthA metal oxides, magnesia, alumina, etc., in

amounts of about -.5'10%,. Thus cobalt catalysts promoted with' thoria and/or magnesia have been used at relatively low pressures of' about 15-75 p. s. i. g. and relatively low temperatures of about 350-450 F. and high HzrCO ratio `of 2 or more to produce a substantially saturated hydrocarbon material from which valuable diesel fuels, lubricating oils, and waxes may be obtained. Iron-type catalysts, usually promoted with a suitable alkali metal compound, such as carbonates, halides, etc., of potassium or sodium may be used in combination with relatively high pressures up to- 60G-700 p. s. i. g. and temperatures of l5W-i750" F., land lower HzzCO ratios generally not above 2, to produce predominantly unsaturated material from which large propori tions of high 'octane' motor'fuelsl may .be recovered.

`While it has thus been possible' to obtainl high octane motor fuels in good yields by this process,

it has also been found that operations under conditions that favor good yields of useful (i. e., C44-oil) products are accompanied by excessive deposition of carbon andV carbonaceous material upon the catalyst. This carbon deposition is a serious problem, particularly when the catalytic operation is carried out by the fluid catalyst technique, which latter because of better heat distribution, transfer and control and because of the, more intimate mixing and contact of the catalyst with the reactants, is considered far superior to xed bed processes for effecting the catalytic synthesis -of hydrocai-lagons.` However,4 two lproblerrlws, that arise in s claims. (c1. 26o-449.6)

conjunction with the fluid solids type of oper-- ation `are the fouling and consequent inactivation ofthe catalyst by carbon deposition, and

the tendency of catalyst particles to disintegrate,

ious proportions of hydrogen and carbon oxides,

presumably as a result of the carbon formation and deposition. Carbon deposition and catalyst disintegration not only 'cut down product yield but cause poor uidization of the catalyst, exicessive fines formation, agglomeration and conditions requiring shut down of the plant.

It has heretofore been found that the tendency for carbonaceous material to deposit `on the cat-` alyst and for catalysts'to disintegrate may be` related to certain operating variables. Thus it is known that relatively fresh'synth'esi's catalyst4 tends to deposit carbon at a substantiallyhigher rate than catalyst that has been resident in the system for a y relatively longer period of time. It is also known that theV carbon formation tendencies and characteristics ofI a catalyst can be` controlled and minimized to a considerable extentby increasing the partial pressure of the hydrogen fed to the hydrocarbon synthesis zone.

down the yields of useful synthesis products and.`

Thus, typical experimental data have shown that,

at a hydrogen partial pressure of about p. s. i.,

an iron synthesis catalyst, such as an alkali metal promoted pyrites ash catalyst, will yield, n

when it has an average age or residence time under synthesis conditions of 0-.75,hours, about 2,2 grams of carbon per,m3( I-I2+CO) consumed.

When the average catalyst age has increased to 'T5-400 hours, the carbon figure drops to about` 1.4. If the catalyst age forthesame catalyst averages 400+ hours, the rate of carbon formation drops to about 0.4 gram. Again, for a given age catalyst, as it has been pointed out, the rate ofy carbon formation decreaseswith increase in hydrogen partial pressure in ,the system. Thus, at a catalyst age averaging 'l5-400 hours under synthesis conditions and operating under hydrogen partial pressure ofabout 100 p. s. i. in.

the synthesis reactor, carbon was deposited at the rate of about 3.2 grams per cubic meter of Hz-l-CO consumed. Operating, at p. s..i. re duced this figure to 0.9 gram, Aand at 240 p. s. i.,

to about 0.6 gram. I

Unfortunately, desirable as it is to keep carbon formationat a low rate it has been found hitherto that, in general, these factors favoring low rate o-f -carbon formation alsotend to keep ,t conversely, those l operating conditions which 3 favor high yields of C4+ hydrocarbons also favor formation ofI excessive amounts". of carbon.

55 Thus, as indicated, when the hydrogen partial pressure in the synthesis feed gas is increased to, say, about 200 psi., by raising the ratio of hydrogen in the feed, the selectivity to liquid hydrocarbon of the gasoline range is generally low. Similarly if, as a result of feeding fresh feed and recycle tail gas, the ratio of hydrogen to the total constituents of the gas feed, or Hz/Hz-I-CO-i-COZ ratio "is low, the selectivity to useful products is high, but the rate of carbon formation also is excessive. Again, as has beenv pointed out, fresh catalyst is highly.V reactivebut tends to form large quantities of 'carbon wheref as, under the same reaction conditions, aged' catalyst produces less carbon but` also less C4+ oil. Again those hydrocarbon. synthesis catalysts that are active and give high yields of C4+ products also form largefquantitiesofcarbon, and those synthesis catalysts which deposit low quantities of carbon under normal synthesis conditions generally have a low selectivity to useful liquid synthesis products.

It is; therefore, :the principal. object. of thepres.- ent `invention to provide ani` improved process forv the conversion of GO andzI-Iz to. form highv yieldsV of normally liquid hydrocarbonY without forming excessivek amountsof carbon during the conversion and without. excessivefragmentation ofthe catalyst.

Other and more-specific objectsaand advan tages of the inventionw will appear hereinafter.

It has now beenifoundzthat-highyields of useful synthesis products. unaccompaniedn by excessive carbon formation` and.- catalyst disintegration may be obtained vby'operatingathydrocarbon synthesis.r plant `comprising two synthesisfreaction stages', using-acatal-ystof low activity in the Y first reactor, followed by a catalyst of, rela tively high activity inthe second reactor operating at substantially higher pressure thanthe. vfirst reactor.

In accordance with; theinvention, a; catalyst. of high mechanicals-trength; butl of. relatively low activity at ordinary-.synthesis temperatures, such as severelysintered'` red, ironoxide, is employed inthe first stage-,under known` synthesis conditions, such asl-6509 F. and- 400.p.` s i. g., synthesis gas compositionof Hz/.COin thefratio of about 1.0- -1.7, and afrecycle/freshV feedratio of. about 2/1. converstion of about.'.0'80.%.is obtained. Because of the -low conversion..v of theA synthesisfgas the hydrogen partial. pressure. infthe. first stage is comparatively high, inv the. neighborhood of 145-175 pi s.v i.,. thus vfurther decreasing. thev tendencyr for carbon formationin this zone, .as compared to carbon. formation tendencies. atthe normal. conversions. off. 9.0-10,0%, vwhich, obtain with active catalysts; Low activity synthesis catalysts characteristically form` negligible .or only slight. quantities. of carbonin the. course of the reaction and. as 1 a` consequence, .disintegration of the catalyst is. only very slight. Furthermore, this low activity catalyst was. prepared by sintering inY hydrogen at temperatures, of. 15501650 R, aprocedureV which results in a. catalyst which disintegrates muchfless readily than more, active catalysts sinteredlatlower temperatures, v

The second. reaction stage contains amore ac.- tive catalyst; in order toaecomplish ah-igh over'- all conversion ,alkali-metalv promoted Vresintered iron pyrites or ammonia synthesisI type catalysts are suitable; Within the second stage'reaction',v low carbon formation rates are obtainedwithout decreasing selectivities to useful liquid'` hydrocarbons, byr increasing the hydrogen vpartial pres- Under these, conditions, a synthesisAY gas.

4 sure in the feed from the flrst reaction stage by increase of the total pressure Within the second stage reactor` Thus by maintaining the hydrogen partial pressure of about to 240 p. s. i. in the second stage reactor but by increasing the total pressure from the customary or normal range'of 350-450'fp. s. i. g. vto the high pressure range of 600-'700-p. s. i; g., then low carbon formation characteristics of high hydrogen partial pressure operations are obtained even with an Iactive catalyst, but yields and selectivities to useful-products are not decreased as they normally :are under high hydrogen partial pressures. Thusin operating iniaccordance with the present invention, wherein a partial conversion of synthesis gas is obtained in a primary conversion stage under conditions conductive to negligible carbon formation and long catalyst life, and high over-all conversion is obtained by contacting the unconverted gases from the first stage with a more. active catalyst.inthe'secondstage under conditions to give,v high yieldsof useful products and low quantities of carbon deposition, it is now possibleY to overcomexthe catalyst disintegration.

Referring now to. thedrawing, 2represents a.

reactor whichtispreferablyin the forniy cfa ver-1 tical cylinder havingalQWerconical-,section and an upper, expanded section.. A. synthesis feed gas mix-tureof hydrpgenand carbonmonoxide,

inthe ratio of. about. 1,0to 2.0 mols Hz to l` mol CO is introduced into-reactor. 2 through line 4 and ows upwardlyi through. ascreen orA grid 6 to effect good gasdistribution';

Within-reactor.- 2 there-isi disposed a mass of relatively low activity hydrocarbon synthesis catalyst, such as KzCOa-'promoted mill scale or KzCOa-promoted` red riron oxide" severely sintered attemperatures in the range-f of 1550l750 F. This high sintering temperature; produces a catalyst of high' mechanical strength. and' showing a high resistancel toY distintegration; This cat'- alyst is maintainedfin the form'l of a. powder having; a particleV size distribution such that less than 20% of the particlesfhave diameters 0-20 microns; and'less:tl'1an 10%' of the'particles haveV diameters larger: than 8U'microns. This catalyst, which is preferablyv promoted" withA an alkali metal salt, such' as1'05-115'% KzCOa may be supiliedlov reactor 2l from catalysthopper 8 through The .linear velocity-of' the gasesto reactor 2 is maintained' within theiapproxi'mate range of 0.3 to 3.0 feet per second, preferably between 0.5 to.y 1.0 Vfeet perl second. Undei these'l conditions the catalyst in rea-ctorZA assumes the form of a dense; turbulent massresemblingia boiling liquid, with a more or less Well-,defined upper-levert?, and. an apparent density ofabdut 25m-75 lbs/cu. ft. depending upon the iiuidization4v conditions, the lower apparent density beingassociatedwith the higher velocities. fthe-amount ofsynthesis gas supplied through line`j'4 is''sof-controlled that about 5- to- 20 normal cubiclfeetof Hz-IeCO. enter reactor Y2 per pound ofcatr'ilystV per hour.:

Within reactcr2-the"total pressureis adjusted `to 'about-l 3504-45r`p:s.'V i; gl, with a'recycle tail gas to fresh feed ratio of about 2 to l. The reac-Y tion temperature maybe controlled by any convenient means, such as a cooling jacket or coil (not shown) inside or outside react-or 2. The temperature within the uidized mass is kept uniform at about 625 to 675 F., and under these conditions a synthesis gas conversion of about 75% is obtained. At this relatively low conversion level, a hydrogen partial pressure of about 150-175 p. s. i. obtains in reactor 2.

When entering the enlarged section of reactor 2 the gas velocity is suiciently decreased so that the gases will no longer support any substantial quantity of catalyst, and most ofthe catalyst particles entrained in the upowing gases drop back into the luidized mass. The volatile reaction products and unreacted gases, containing only small quantities of entrained catalyst are passed through a gas-solids separator I4, such as one or more cyclones, filters, etc. This removes all but traces of entrained fines, and the fines thus removed may be returned through line I6 to the fluidized bed in reactor 2.

Product vapors and gases comprising unreacted CO and H2 may be withdrawn through line I8 and passed through cooler II to high pressure separator I3 wherein normally condensible hydrocarbons, Ioxygenated products, and water condense and settle. These latter may be removed via line I5 and sent to the liquid products recovery system. Unreacted synthesis gases comprising H2 and CO, and uncondensed light hydrocarbons are withdrawn overhead from separator I3 via line I1, a portion recycled to reactor 2 via line I9 and recycle pump 2|, and the balance passed to compressor 20, compressed to a pressure of about 650 p. s. i. g. and passed to the bottom of fluid reactor 24 via line 22. The latter is essentially of similar design to reactor 2, but is operated under different synthesis conditions. Within reactor 24 there is disposed a dense fluidized bed of an active hydrocarbon synthesis catalyst, such as ammonia synthesis catalyst or resintered iron pyrites ash preferably promoted with 0.5-1.5% KzCOa, and having essentially the same particle size distribution as the catalyst in reactor 2. This catalyst is admitted from hopper 26 via line 28. The reaction conditions prevailing within reactor 24 are preferably a temperature in the range of from about 650750 F., a pressure of about 550-750 p. s. i. g., a synthesis gas feed rate of about 15-25 cubic feet/hour/pound catalyst, a recycle rate of 2, linear 'velocity of about` 0.7 to 3.0 feet per second. Under these reaction conditions, and in consequence of the 70 to 80% conversion level of synthesis gas in reactor 2 the hydrogen-partial pressure in reactor' 24 is about 185-240 p. s. i., whereas the hydrogen concentration in the feed gas to reactor 24, or Hz/Hz-I-CO-i-COZ ratio, is about 0.40. Thus in the second reactivestage, by maintaining a relatively high hydrogen partial pressure of about 185 to 240 p. s. i., by increasing the total pressure from the 400 p. s. i. g. level in reactor 2 to the high pressure level of 600L700'ps'. i. g. in reactor 24, the low carbon formation characteristics of high hydrogen partial pressures operation are obtained, and yields and selectivities to useful products are not decreased as they normally are under high hydrogen partial pressures.

As in the case of reactor 2, product vapors and gases are passed upwardly through gassolids separator 30, then are withdrawn through line 32, cooler 34, and line 3B` to separator 38,'l

where liquid products may be removed and separated from the tail gas. Liquid products may be withdrawn through line 40 for process ing by any method known in the art, such as distillation, extraction, catalytic reforming, etc. Tail gas may be withdrawn overhead through line 42 and be recycled to reactor 24 through lines 44 and 46. Y

The invention iadmits of numerous modifications obvious to those skilled in the art. Instead of employing two different species of catalysts in the two stages, it may be desirable to use only one kind of catalyst in the system, but at different activity levels. Thus it has already been disclosed that aged catalyst is less active than relatively fresh catalyst and so it may be desirable under certain conditions to maintain a fluid bed of aged catalyst, such as red iron oxide, in reactor 2 land a bed of relatively fresh catalyst of the same species in reactor 24.

In accordance with the reaction condition disclosed, the feed from the'iirst synthesis stage is converted to the extent of about in the second synthesis zone, making an overall con version level of synthesis gas of about By operating in accordancel with this invention, it is now possible to employ a feed of relatively low Hz/CO ratio, such as 1.5/1, which ordinarily gives high yields of 04+ products but also deposits large quantities of carbon on the catalyst, and obtain good selectivity to useful products Without excessive carbon deposition and conse'- quent catalyst fragmentation.

The following illustrative data are included in order to indicate operating conditions and yields representative of this invention.

lst Stage- KSglerled 2nd Stager 3 ro- Ammonia Gatalyst mote-ci Red Synthesis Iron Oxide Catalyst Catalyst Avg. Cat. Temp., 650 650 S. c. t. h./1b. Cat. (C-i-O free bas1s). 10.0 20,0 Recycle Ratio 2. 8 2. 0 Fresh Feed Hs/CO Ratio. l. l 1.4 Pressure, p. s. i. g...... 400 650 Inlet Velocity, it./sec..- 0. 4 1.0 Hg/Hz-l-CO-I-COQ in tota-llecd. O. 40 O. 30 H1 Partial Pressure, p. s. 1....... 148 191 Hz-l-CO Conversion. vol. percent 79. 7 00 0 2(98. 0) Liquid Yields, cclm of Conv.

Hz-I-CO Cl-i-Oxl. 176 172 Cri-Oil-l-Oxy. Cpds. in H2O Layer. 215 197 Cs Oil 239 235 Carbon Formation, gm

2 OO 0.5 0.9 Exit Gas Composition, vo perce H2, vol. percent... 1 30.0 27. 5 CO, vol. percent.. 22. 0 6.9 CO2, vol. percent... 32. 3 39. 8 CH; vol. percent... 4.2 C?, vol. percent 3. 6

l Fused magnetite admixed with minor amounts of alumina and potassium promoter, and reduced..

2 Hz-l-CO conversion in second stage operation-of 90.0% represents an overall HTI-CO conversion of 98.0%.

3 Exit gas from stage l is fresh feed for stage 2.

The data'in the first column are pilot plantv results obtained with a KzCOsV promoted red iron oxide catalyst which had been sintered in H2 at 1570 F. The low conversion of 79.7 volume percent is typical of catalyst sintered at a very high temperature. The C4+ oil yield was 176 cc./m3 of converted Hz-ICO. The carbon formation was only 0.5 gmL/m:i of converted feed; the carbon content of the catalyst was 6.1% after 235 hours. 'I'he low carbon formation is characteristic 0f this severely sintered catalyst 7.-. and represents about 50% tion that. would be predicted for a more. active. catalyst produced by sintering at 1500 F. or lower. After 235 hours of operation the -40 micron fraction of` this catalyst increased from l0 to i7 weight percent and then to 20 weight peiCntafter 451 hours indicating good mechanicalA strength.

If now the exit gas from theY first stage is passed to a second reactor containing ammonia synthesis catalyst, a conversion of 90% is readily obtained in this reactor because of the high activity of this catalyst, In this Way, a high conversion of 98% on thel original synthesis gas is obtained. By` increasing voperating pressure to 650Y p. s. i. g., carbon formation is maintained at a reasonabley level (0.9 gm./m3 of Hz-l-CO converted) in this clean-up reactor. Since this reactor operates on tail gas from the rst stage, the size of the second high pressure reactor is smaller than the 1st stage reactor (in the order of 1/5 the size) As indicatedV above, in the two-stage operation, by using the severely sintered catalyst in stage one, carbon formation is roughly 50% of that normally obtained with active catalyst. In the second stage wherein synthesis operation is carried out on the remaining of the original synthesis feedgas unconverted in they first stage, carbon formation based on the feed to the second stage isequivalent to that normally obtained high pressure operation. However, since only 20% of the total feedgas is treated in the second stage, and since in the iii-st stage, wherein 80% of the synthesis gas was converted, onlyI 50% of the usual carbon deposition took place, an over-all net decrease of about 60% in carbon formation is realized when operating in accordance with the present invention.

l't is to be understood that the term active or inactive catalyst refers to the activity of a given catalyst under the synthesis condition, such as temperature and pressure, prevailing in the synthesis reaction zone.

While the foregoing description has served to illustrate specio applications and results of the invention, other modifications obvious to those skilled inthe art are within its scope.

What is claimed is:

1. An improved process for producing valuable conversion products from CO and H2 by a catalytic synthesis reaction without excessive deposi tion of solid carbonaceous material in the course of said synthesis which comprises' contacting a synthesis feed gas mixture containing H2 and CO in the ratio of about 1.0-1.5:1 at a temperature of about 650 to 700 F. with a dense, turbulent mass of finely divided potassium salt promoted iron hydrocarbon synthesis catalyst of relatively low activity under the synthesis conditions prevail-ing in said zone, maintaining a total pressure of about S50-450 p. s. i. g. within said zone, maintaining a hydrogen partial pressure of about 150 to 175 p. s. i. Within said Zone, maintaining a synthesis gas conversion level of about 70-80% within said.v zone, withdrawing reaction products offthecarbon I Olmaand. unreacted gases. from. Said.. zone.. and. passing.

unreacted carbon monoxide and hydrogen. with.-

drawn. from saidrst Zone to. a second synthesis Zone. maintaining aV total pressure 'of 60o-750 D. s. i. g. andatempelatlire level of from about 650to about. 700? F. in said second reaction zone, maintaining, a. dense fiuidized Ibed of iron type potassium-,promoted yhyclrocarbon synthesis catalyst O f high activity under the synthesis conditions prevailing` in saidsecond zone,y contacting the.' Ieactantswith said catalyst for a sufcient period Qi. time to4 attain the desired conversion,

and recovering a product containing substantial. amounts. o hydrocarbons boiling in the gasoline range from both .reaztioriy zcnea 2; The. processV of Claim l wherein the feed rate of said synthesis gas. mixture to said primary zone-s about 10--20 cubic feet per pound of catalyst perhoui. and the, rate of feed gas to said second. reaction` ZoneiS.. about 2.0.-30 Y cubic feet per pound catalyst perA hour.

3; An imprOVCClDlOess for-producing valuable conversion; products from CO and H2 by a catalytic synthesis reaction without excessive deposi tion of carborltceous material in the course of saidY synthesis, which comprises contacting a synthesis feed gas mixturev containing H2 and CO in the ratio of` about l.0:1.5 to l at a temperatllle of about 650 to 700o F. with a dense turbulent mass o rlelydivided potassium carbonate plomoteolV red iron oxide catalyst sintered at a. temperature. above about 1550 F. in an atmosphere of hydrogen, .maintaining a total msureof about 350 to 450 p. s. i. g. within said zone, maintaining ahydrogen partial pressure of about. 1 50 to 175 p, s. i. within said zone, main-- taining a Synthesis gas conversion level of about 7.0 to within said zone, withdrawing reaction products .and unlcaotedgases. from said zone and passing unreacted CO` and Hg withdrawn fr QIIl Sadlt zone to a second synthesis zona maintaining a total pressure of about 500 to 750 p, s. i, g. and a temperature level of about 65) to about 700 F. insa-id second reaction zone, maintaining a dense fluidized bed of ammonia synthesis catalyst in said second zone, contacting the reactants with said catalyst to attain a high conversion level in said zone, and recovering a product containing substantial amounts of hydrocarbons boiling in the gasoline range from both reaction zones.

CLINTON n. nonnen.

REFERENCES CITED .The following references are of record in the file of this patent;

UNITED STATES PATENTS Number Name Date 2,178,824 Atwell Nov. 7, i939 2,244,196 Herbert June 3, 1941 2,417,164 Huber Mar. 11, 1947 2,445,796 Millendorf July 27, 1946 2,451,879. Scharrnann Oct. '19, 1948 2,461,570 Roberts' Feb. l5, i949 2,467,802 Barr Apr. 1S, 1949 

1. AN IMPROVED PROCESS FOR PRODUCING VALUABLE CONVERSION PRODUCTS FROM CO AND H2 BY A CATALYTIC SYNTHESIS REACTION WITHOUT EXCESSIVE DEPOSITION OF SOLID CARBONACEOUS MATERIAL IN THE COURSE OF SAID SYNTHESIS WHICH COMPRISES CONTACTING A SYNTHESIS FEED GAS MIXTURE CONTAINING H2 AND CO IN THE RATIO OF ABOUT 1.0-1.5:1 AT A TEMPERATURE OF ABOUT 650* TO 700* F. WITH A DENSE, TURBULENT MASS OF FINELY DIVIDED POTASSIUM SALT PROMOTED IRON HYDROCARBON SYNTHESIS CATALYST OF RELACTIVELY LOW ACTIVITY UNDER THE SYNTHESIS CONDITIONS PREVAILING IN SAID ZONE, MAINTAINING A TOTAL PRESSURE OF ABOUT 350-450 P. S. I. G. WITHIN SAID ZONE, MAINTAINING A HYDROGEN PARTIAL PRESSURE OF ABOUT 150 TO 175 P. S. I. WITHIN SAID ZONE, MAINTAINING A SYNTHESIS GAS CONVERSION LEVEL OF ABOUT 70-80% WITHIN SAID ZONE, WITHDRAWING REACTION PRODUCTS AND UNREACTED GASES FROM SAID ZONE AND PASSING UNREACTED CARBON MONOXIDE AND HYDROGEN WITHDRAWN FROM SAID FIRST ZONE TO A SECOND SYNTHESIS ZONE, MAINTAINING A TOTAL PRESSURE OF 600-750 P. S. I. G. AND A TEMPERATURE LEVEL OF FROM ABOUT 650 TO ABOUT 700* F. IN SAID SECOND REACTION ZONE, MAINTAINING A DENSE FLUIDIZED BED OF IRON TYPE POTASSIUM PROMOTED HYDROCARBON SYNTHESIS CATALYST OF HIGH ACTIVITY UNDER THE SYNTHESIS CONDITIONS PREVAILING IN SAID SECOND ZONE, CONTACTING THE REACTANTS WITH SAID CATALYST FOR A SUFFICIENT PERIOD OF TIME TO ATTAIN THE DESIRED CONVERSION, AND RECOVERING A PRODUCT CONTAINING SUBSTANTIAL AMOUNT OF HYDROCARBONS BOILING IN THE GASOLINE RANGE FROM BOTH REACTION ZONES. 